Acid-reactive dental fillers, compositions, and methods

Abstract

Acid-reactive dental fillers, and methods of making and using such fillers, are disclosed. The acid-reactive dental fillers include a trivalent metal, oxygen, fluorine, an alkaline earth metal, and, optionally, silicon. The acid-reactive dental fillers are preferably nanostructured, for example, in the form of nanoparticles.

What is claimed is: 
     
       1. A composition comprising an oxyfluoride material;
 wherein the oxyfluoride material is acid-reactive, non-fused, and comprises a trivalent metal, oxygen, fluorine, and an alkaline earth metal; and 
 wherein the composition is a dental filler. 
 
     
     
       2. The composition of  claim 1  wherein the trivalent metal is selected from the group consisting of aluminum, lanthanum, and combinations thereof. 
     
     
       3. A composition comprising an oxyfluoride material;
 wherein the oxyfluoride material is acid-reactive, non-fused, and comprises aluminum, oxygen, fluorine, and an alkaline earth metal; and 
 wherein the composition is a dental filler. 
 
     
     
       4. The composition of  claim 3  wherein at least 90% by weight of the oxyfluoride material is nanostructured. 
     
     
       5. The composition of  claim 4  wherein at least 90% by weight of the oxyfluoride material is in the form of nanoparticles. 
     
     
       6. The composition of  claim 5  wherein the nanoparticles are non-aggregated. 
     
     
       7. The composition of  claim 5  wherein the nanoparticles are aggregated. 
     
     
       8. The composition of  claim 5  wherein the nanoparticles have an average size of at most 100 nanometers. 
     
     
       9. The composition of  claim 4  wherein the oxyfluoride material is in the form of a coating on a particle. 
     
     
       10. The composition of  claim 9  wherein the particle is a nanoparticle. 
     
     
       11. The composition of  claim 9  wherein the particle comprises a metal oxide. 
     
     
       12. The composition of  claim 11  wherein the metal oxide is silica. 
     
     
       13. The composition of  claim 4  wherein the oxyfluoride material is in the form of a coating on an aggregate of particles. 
     
     
       14. The composition of  claim 13  wherein the particles comprise nanoparticles. 
     
     
       15. The composition of  claim 13  wherein the particles comprise a metal oxide. 
     
     
       16. The composition of  claim 15  wherein the metal oxide is silica. 
     
     
       17. The composition of  claim 4  wherein the oxyfluoride material is infiltrated in a porous structure. 
     
     
       18. The composition of  claim 17  wherein the porous structure comprises a porous particle. 
     
     
       19. The composition of  claim 18  wherein the porous particle comprises a metal oxide. 
     
     
       20. The composition of  claim 19  wherein the metal oxide is silica. 
     
     
       21. The composition of  claim 17  wherein the porous structure comprises a porous aggregate of particles. 
     
     
       22. The composition of  claim 21  wherein the particles are nanoparticles. 
     
     
       23. The composition of  claim 21  wherein the particles comprise a metal oxide. 
     
     
       24. The composition of  claim 23  wherein the metal oxide is silica. 
     
     
       25. The composition of  claim 17  wherein the porous structure comprises a porous coating. 
     
     
       26. The composition of  claim 3  wherein the oxyfluoride material further comprises silicon. 
     
     
       27. The composition of  claim 3  wherein the oxyfluoride material further comprises a heavy metal. 
     
     
       28. The composition of  claim 27  wherein the heavy metal is zirconium. 
     
     
       29. The composition of  claim 3  wherein the molar ratio of aluminum to the alkaline earth metal in the oxyfluoride material is at least 50:50 and at most 95:5. 
     
     
       30. The composition of  claim 3  wherein the molar ratio of oxygen to fluorine in the oxyfluoride material is at least 50:50 and at most 95:5. 
     
     
       31. The composition of  claim 3  wherein the alkaline earth metal is selected from the group consisting of strontium, calcium, barium, and combinations thereof. 
     
     
       32. A composition comprising an oxyfluoride material;
 wherein the oxyfluoride material is acid-reactive and comprises a trivalent metal, oxygen, fluorine, and an alkaline earth metal, with the proviso that the oxyfluoride material comprises at most 25 mole % silicon based on the total moles of silicon, the trivalent metal, the alkaline earth metal, and any additional cations; and 
 wherein the material is a dental filler. 
 
     
     
       33. The composition of  claim 32  wherein the trivalent metal is selected from the group consisting of aluminum, lanthanum, and combinations thereof. 
     
     
       34. The composition of  claim 32  wherein the trivalent metal is aluminum. 
     
     
       35. The composition of  claim 34 , with the proviso that the oyxfluoride material comprises at most 20 mole % silicon, based on the total moles of silicon, aluminum, and the alkaline earth metal. 
     
     
       36. A dental filler prepared by a method comprising:
 combining a first liquid composition comprising a source of a trivalent metal and a source of an alkaline earth metal with a second liquid composition comprising a source of fluorine to provide an acid-reactive oxyfluoride material, wherein the oxyfluoride material comprises the trivalent metal, oxygen, fluorine, and the alkaline earth metal; and 
 separating the oxyfluoride material from the combined liquid compositions to provide the dental filler. 
 
     
     
       37. The dental filler of  claim 36  wherein the trivalent metal is selected from the group consisting of aluminum, lanthanum, and combinations thereof. 
     
     
       38. The dental filler of  claim 36  wherein the trivalent metal is aluminum. 
     
     
       39. A method of preparing a dental filler comprising:
 combining a first liquid composition comprising a source of a trivalent metal and a source of an alkaline earth metal with a second liquid composition comprising a source of fluorine to provide an acid-reactive oxyfluoride material, wherein the oxyfluoride material comprises the trivalent metal, oxygen, fluorine, and the alkaline earth metal; and 
 separating the oxyfluoride material from the combined liquid compositions to provide the dental filler. 
 
     
     
       40. The method of  claim 39  wherein the trivalent metal is selected from the group consisting of aluminum, lanthanum, and combinations thereof. 
     
     
       41. A method of preparing a dental filler comprising:
 combining a first liquid composition comprising a source of aluminum and a source of an alkaline earth metal with a second liquid composition comprising a source of fluorine to provide an acid-reactive oxyfluoride material, wherein the oxyfluoride material comprises aluminum, oxygen, fluorine, and the alkaline earth metal; and 
 separating the oxyfluoride material from the combined liquid compositions to provide the dental filler. 
 
     
     
       42. The method of  claim 41  wherein the oxyfluoride material is nanostructured. 
     
     
       43. The method of  claim 41  wherein at least one of the liquid compositions further comprises a source of hydroxide as a source of oxygen. 
     
     
       44. The method of  claim 43  wherein the source of hydroxide is selected from the group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide, and combinations thereof. 
     
     
       45. The method of  claim 41  wherein at least one of the liquid compositions is an aqueous composition having a pH greater than 7. 
     
     
       46. The method of  claim 41  further comprising drying the separated oxyfluoride material at a temperature of at most 350° C. 
     
     
       47. The method of  claim 46  wherein drying is at a temperature of at most 250° C. 
     
     
       48. The method of  claim 47  wherein drying is at a temperature of at most 150° C. 
     
     
       49. The method of  claim 41  wherein combining provides an oxyfluoride material in a form selected from the group consisting of a precipitate, a coating on a particle, a coating on an aggregate of particles, a material infiltrated in a porous structure, and combinations thereof. 
     
     
       50. The method of  claim 41  wherein separating the oxyfluoride material comprises filtering the oxyfluoride material. 
     
     
       51. The method of  claim 41  wherein the source of aluminum is selected from the group consisting of aluminum nitrates and basic or oxy salts thereof, aluminum carboxylates and basic or oxy salts thereof, aluminum halides and basic or oxy salts thereof, and combinations thereof. 
     
     
       52. The method of  claim 41  wherein the source of aluminum comprises an aluminum alkoxide. 
     
     
       53. The method of  claim 52  wherein the aluminum alkoxide is selected from the group consisting of aluminum isopropoxide, aluminum sec-butoxide, and combinations thereof. 
     
     
       54. The method of  claim 41  wherein the source of fluorine is selected from the group consisting of ammonium fluoride, ammonium hydrogen difluoride, hexafluorosilicic acid and salts thereof, and combinations thereof. 
     
     
       55. The method of  claim 41  wherein the source of the alkaline earth metal comprises strontium nitrates, strontium carboxylates, strontium halides, calcium nitrates, calcium carboxylates, calcium halides, and combinations thereof. 
     
     
       56. The method of  claim 41  wherein the second liquid composition further comprises a source of silicon. 
     
     
       57. The method of  claim 56  wherein the source of silicon comprises sodium silicate, hexafluorosilicic acid and salts thereof, silicon alkoxides, and combinations thereof. 
     
     
       58. The method of  claim 41  wherein at least one of the first and second liquid compositions further comprises water. 
     
     
       59. The method of  claim 41  further comprising dispersing the separated oxyfluoride material in a liquid medium. 
     
     
       60. The method of  claim 59  wherein the liquid medium comprises water. 
     
     
       61. The method of  claim 59  further comprising coating the dispersed oxyfluoride material on a particle, coating the dispersed oxyfluoride material on an aggregate of particles, infiltrating the dispersed oxyfluoride material in a porous structure, or combinations thereof. 
     
     
       62. A method of preparing a dental filler comprising:
 providing a porous structure; 
 infiltrating a first liquid composition comprising a source of a trivalent metal and a source of an alkaline earth metal in the porous structure; and 
 infiltrating a second liquid composition comprising a source of fluorine in the porous structure to provide a porous structure infiltrated with an acid-reactive oxyfluoride material, wherein the acid-reactive oxyfluoride material comprises the trivalent metal, oxygen, fluorine, and the alkaline earth metal. 
 
     
     
       63. The method of  claim 62  wherein the trivalent metal is selected from the group consisting of aluminum, lanthanum, and combinations thereof. 
     
     
       64. A method of preparing a dental filler comprising:
 providing a porous structure; 
 infiltrating a first liquid composition comprising a source of aluminum and a source of an alkaline earth metal in the porous structure; and 
 infiltrating a second liquid composition comprising a source of fluorine in the porous structure to provide a porous structure infiltrated with an acid-reactive oxyfluoride material, wherein the acid-reactive oxyfluoride material comprises aluminum, oxygen, fluorine, and the alkaline earth metal. 
 
     
     
       65. The method of  claim 64  further comprising drying the porous structure infiltrated with the acid-reactive oxyfluoride material at a temperature of at most 350° C. 
     
     
       66. The method of  claim 64  wherein infiltrating the first liquid composition is carried out before infiltrating the second liquid composition. 
     
     
       67. The method of  claim 64  wherein infiltrating the first liquid composition is carried out after infiltrating the second liquid composition. 
     
     
       68. The method of  claim 64  wherein the second liquid composition further comprises a component selected from the group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide, and combinations thereof. 
     
     
       69. The method of  claim 64  wherein the second liquid composition further comprises a source of silicon. 
     
     
       70. The method of  claim 64  wherein at least one of the first and second liquid compositions further comprises water. 
     
     
       71. The method of  claim 64  wherein the porous structure is selected from the group consisting of porous particles, porous aggregates of particles, and combinations thereof. 
     
     
       72. A dental composition comprising a hardenable resin and a dental filler according to  claim 1 . 
     
     
       73. A dental composition comprising a hardenable resin and a dental filler according to  claim 3 . 
     
     
       74. The dental composition of  claim 73  wherein the hardenable resin comprises a polymerizable ethylenically unsaturated compound. 
     
     
       75. The dental composition of  claim 74  wherein the hardenable resin further comprises an acid. 
     
     
       76. The dental composition of  claim 73  wherein the composition is in the form of a single-part dental composition. 
     
     
       77. The dental composition of  claim 73  wherein the composition is in the form of a multi-part dental composition. 
     
     
       78. The dental composition of  claim 77  wherein the multi-part composition comprises a first part and a second part, and wherein each part is independently selected from the group consisting of a liquid, paste, gel, or powder. 
     
     
       79. The dental composition of  claim 77  wherein the multi-part composition is selected from the group consisting of a paste-paste composition, a paste-liquid composition, a paste-powder composition, and a powder-liquid composition. 
     
     
       80. The dental composition of  claim 73  wherein the composition is selected from the group consisting of dental adhesives, cavity liners, cements, coatings, orthodontic adhesives, restoratives, sealants, and combinations thereof. 
     
     
       81. The dental composition of  claim 73  wherein at least 90% by weight of the oxyfluoride material is nanostructured. 
     
     
       82. The dental composition of  claim 81  further comprising a non acid-reactive filler. 
     
     
       83. The dental composition of  claim 82  wherein at least 75% by weight of the total filler in the dental composition is nanofiller. 
     
     
       84. The dental composition of  claim 82  wherein at least 90% by weight of the total filler in the dental composition is nanofiller. 
     
     
       85. The dental composition of  claim 73  wherein the composition is in the form of a paste. 
     
     
       86. A dental composition comprising a hardenable resin and a dental filler according to  claim 32 . 
     
     
       87. The dental composition of  claim 86  wherein the composition is in the form of a paste. 
     
     
       88. A dental composition comprising at most 15% by weight of a dental filler according to  claim 1 , with the proviso that the dental filler provides at least 2 square meters of surface area per gram of the dental composition. 
     
     
       89. A dental composition comprising:
 at most 10% by weight of a dental filler according to  claim 1 , based on the total weight of the dental composition; and 
 at least 40% by weight of additional fillers, based on the total weight of the dental composition. 
 
     
     
       90. A method of preparing a dental composition comprising combining a dental filler according to  claim 1  and a hardenable resin. 
     
     
       91. A method of preparing a dental composition comprising combining a dental filler according to  claim 3  and a hardenable resin. 
     
     
       92. A method of preparing a dental composition comprising combining a dental filler according to  claim 32  and a hardenable resin. 
     
     
       93. A dental composition comprising:
 a dental filler according to  claim 1 ; 
 a polyacid; and 
 water. 
 
     
     
       94. A dental composition comprising:
 a dental filler according to  claim 3 ; 
 a polyacid; and 
 water. 
 
     
     
       95. A multi-part dental composition comprising:
 a part A comprising a dental filler according to  claim 1 ; and 
 a part B comprising a polyacid. 
 
     
     
       96. A multi-part dental composition comprising:
 a part A comprising a dental filler according to  claim 3 ; and 
 a part B comprising a polyacid. 
 
     
     
       97. The multi-part dental composition of  claim 96 , wherein at least 90% by weight of the oxyfluoride material is nanostructured. 
     
     
       98. The multi-part dental composition of  claim 96  wherein at least one of part A or part B further comprises an additional acid reactive filler. 
     
     
       99. The multi-part dental composition of  claim 96  wherein at least one of part A or part B is in the form of a liquid or a paste. 
     
     
       100. The multi-part dental composition of  claim 99  wherein part A and part B are provided in a unit-dose capsule. 
     
     
       101. The multi-part dental composition of  claim 99  wherein part A and part B are each independently in the form of a liquid or a paste. 
     
     
       102. The multi-part dental composition of  claim 101  further comprising a dual barrel syringe having a first barrel and a second barrel, wherein the part A resides in the first barrel and the part B resides in the second barrel. 
     
     
       103. The multi-part dental composition of  claim 101  wherein part A and part B can be mixed in a static mixer. 
     
     
       104. The multi-part dental composition of  claim 96  further comprising water residing in at least one of part A or part B. 
     
     
       105. The multi-part dental composition of  claim 96  further comprising a polymerizable component residing in at least one of part A or part B. 
     
     
       106. The multi-part dental composition of  claim 105  wherein the polyacid and the polymerizable component are the same. 
     
     
       107. The multi-part dental composition of  claim 105  wherein the polyacid and the polymerizable component are different. 
     
     
       108. The multi-part dental composition of  claim 96  further comprising a non acid-reactive dental filler residing in at least one of part A or part B. 
     
     
       109. The multi-part dental composition of  claim 108  wherein at least 90% by weight of the non acid-reactive dental filler is in the form of nanoparticles. 
     
     
       110. The multi-part dental composition of  claim 108  wherein the non acid-reactive dental filler comprises a metal oxide. 
     
     
       111. The multi-part dental composition of  claim 110  wherein the metal oxide is silica. 
     
     
       112. A multi-part dental composition comprising:
 a part A comprising an acid-reactive dental filler according to  claim 32 ; and 
 a part B comprising at least one polyacid. 
 
     
     
       113. A method of using a multi-part dental composition according to  claim 95  comprising:
 mixing a quantity of part A and a quantity of part B to form a dental composition; and 
 applying the dental composition to a surface. 
 
     
     
       114. A method of preparing a dental article comprising:
 combining a dental filler according to  claim 1  and a hardenable resin to form a dental composition; and 
 hardening the composition to fabricate a dental article selected from the group consisting of crowns, fillings, mill blanks, orthodontic devices, and prostheses. 
 
     
     
       115. A method of preparing a dental article comprising:
 combining a dental filler according to  claim 3  and a hardenable resin to form a dental composition; and 
 hardening the composition to fabricate a dental article selected from the group consisting of crowns, fillings, mill blanks, orthodontic devices, and prostheses. 
 
     
     
       116. A method of preparing a dental article comprising:
 combing a dental filler according to  claim 32  and a hardenable resin to form a dental composition; and 
 hardening the composition to fabricate a dental article selected from the group consisting of crowns, fillings, mill blanks, orthodontic devices, and prostheses.